Mechanism of Transition between Cellulose I and

Cellulose I1 during Mercerization

MITSUO TAKAI* and J. ROSS COLVIN, Diuision of Biological Sciences,
National Research Council of Canada, Ottawa, Canada K l A OR6

Synopsis
It is suggested that the transformation from cellulose I to cellulose I1 during mercerization is the
result of a progressive shift of the sheets of cellulose chains within the crystallites of a microfibril
from the quarter-staggered relation in cellulose I to complete correspondence in cellulose 11.
Qualitatively, the results of such a shift would be consistent with the observed increases in lateral
disorder, changes in cell dimensions, swelling, changes in infrared absorption, increases in reactivity
of hydroxyl groups and especially with changes in the relative intensities of meridional, x-ray dif-
fraction reflections of cellulose fibers. The consequences of such a shift also include variations of
the dihedral angle at the glycosidic linkage to provide an opportunity for the conformational changes
which have been deduced from Raman and infrared spectra. Such a shift may take place in the
transformation of native celluloses with antiparallel structure as well as those with parallel polarity.
It is consistent with and is ableto explain examples of “memory” of previous treatment in cellulose
samples.

INTRODUCTION
The conversion of native cellulose I into its second most abundant polymorphic
form, cellulose 11,by strong alkali (mercerization) has been investigated thor-
oughly.’ However, despite the considerable body of information on many
properties of the two forms, the molecular mechanism of transition from I to I1
without dissolution is still a subject of study. Warwicker and associates saw the
change from I to I1 as a result of simple rotation of the chains in the sheets of a
microfibril around their axes, under the influence of concentrated alkali.2.3
Hayashi and colleagues, in a series of papers, developed this concept extensively
to include a change in the chain conformation of cellulose I from the “bent” form
to the “bent and twisted” aspect in cellulose II.4 Basing his conclusions on
Raman spectra, Atalla has refined the notion of a conformational change to
comprise only two variations of the dihedral angle at the glycosidic linkage,
corresponding to cellulose I and cellulose II.5 In contrast, Chanzy and Roche6
see the fibrous mercerization of Valonia cellulose microfibrils as involving an
extensive, transient, “shish-kebab,” lamellar recrystallization in which the
lamellae contain cellulose I1 recrystallized by epitaxy on the backbone of the
cellulose I microfibril.
Each of the foregoing mechanisms are able to explain many of the changes in
properties which are observed when cellulose I becomes cellulose I1 without
dissolution (i.e., changes in unit cell dimensions, swelling, increases in lateral
disorder, variations in relative intensity of absorption bands in the infrared,
* Present address: Department of Applied Chemistry, Faculty of Engineering, Hokkaido Uni-
versity, Sapporo, Hokkaido 060, Japan.

Journal of Polymer Science: Polymer Chemistry Edition, Vol. 16, 1335-1342 (1978)
01978 John Wiley & Sons, Inc. 0360-6376/78/0016-1335$01.00
1336 TAKA1 AND COLVIN

increases in reactivity of hydroxyl groups, changes in Raman spectra, and an

inferred change of chain polarity for Valonia cellulose). However, there are some
recognized differences in properties which are not resolved by the postulated
mechanisms. As noted by Hayashi and colleagues,4 there are significant dif-
ferences in the relative intensities of the meridional reflections of fibers prepared
from cellulose I and cellulose 11. Such differences are shown clearly by Jones1
in his Figure 4. Simple twisting, bending, or rotation of the chains in the sheets
of cellulose within the crystallites of a fiber perpendicular to the x-ray beam
would not affect the relative intensities of the meridional reflections and therefore
an additional, molecular modification must be involved. Furthermore, although
shish-kebab formation of lamellar cellulose I1 certainly takes place in Valonia
cellulose microfibrils in which defects have been created by acid hydrolysis,6no
similar change takes place during the straight forward conversion of bacterial
cellulose I to cellulose I1 by 18%NaOH at room temperature (unpublished ob-
servations). It would seem that fibrous mercerization of cellulose by the
shish-kebab mechanism depends on creation of initial defects by prior degra-
dation of the microfibril and therefore this mechanism is not applicable to the
ordinary conversion of cellulose I to cellulose 11.
It is the purpose of this article to suggest that mercerization (cellulose I
cellulose 11) takes place as the result of a progressive, approximately quarter-
-
stagger shift of sheets of cellulose chains within the crystallites of the microfibril
and to indicate that this suggestion is capable of explaining all the changes in
properties of cellulose which occur during the conversion.

MATERIALS AND METHODS

Pellicles of bacterial cellulose were grown under the conditions described

previously7 for 72-96 hr, except that they were grown in 5-cm-diameter Petri
dishes. The bacterial medium was removed by thorough washing in distilled
water before mercerization of the cellulose.
During mercerization, the ratio of the volume of the wet cellulose to the volume
of 18%NaOH was always so low that dilution of the mercerization solution was
negligible. Percentage shrinkage, as the result of mercerization, was defined
as the ratio of the decrease in diameter of the pellicle to the initial diameter
multiplied by lo@ During mercerization, the temperatures were maintained
within l 0 C of the indicated value by a circulating, thermostated, water bath
except for experiments at O'C, where the flasks were immersed in baths of
melting ice.
The x-ray diffraction photographs were taken of each washed, dried pellicle
after mercerization, both parallel to and perpendicular to the plane of the
membrane. Photographs were obtained by using a Philips Norelco microcamera
with flat film, in a Hilger-Watts generator. Nickel-filtered CuKa x radiation
of wavelength 1.54 A was employed with a specimen-to-film distance of 15mm.
The microcamera was not evacuated during the exposures which varied from
50 to 100 hr, depending upon thickness of the specimen.
 MERCERIZATION MECHANISMS 1337

EXPOSITION, RESULTS, AND DISCUSSION

Postulation
A decade ago, Warwicker and associates pointed out that many of the prop-
erties of both native cellulose I and of cellulose I1 from mercerization could be
best understood in terms of sheets of polyglucosan chains bonded later all^.^,^
Recently, Gardner and Blackwell! in a definitive study of the structure of native,
Valonia cellulose, showed that this form of cellulose I is composed of p-1,4-
polyglucosan chains hydrogen-bonded together in sheets in the (020) plane with
van der Waals contacts between successive sheets.* They showed that Valonia
cellulose was composed of parallel chains, but they stressed that because the
hydrogen bonds are completely contained in the (020) plane, the sheetlike
structure is compatible with either parallel or antiparallel chains. Therefore,
both experimental and theoretical evidence is fully consistent with the notion
that native cellulose I is made up of sheets of polyglucosan chains which are held
together in the (020) plane by hydrogen bonds. Each sheet in a crystallite of
cellulose I of Valonia (and therefore each chain within the sheet) is approxi-
mately quarter-staggered with respect to the neighboring sheet.
Unfortunately, no similar unequivocal statement can be made of the structure
of cellulose 11. The recent, very comprehensive investigations which refer to
cellulose I19J0are actually of this form of the substance which is derived from
regenerated celluloses (not mercerized) where the initial structure(s) of the
polymer has been completely dissolved. It is therefore impossible in principle
to relate the observed structure of the reprecipitated material unambiguously
to that of the original fiber. Another recent investigation of mercerized cotton
cellulose regrettably does not lead to a definite conclusion.ll
In the absence of a definitive structure for nonregenerated cellulose I1 (pref-
erably from Valonia), we shall adopt the assumption of Poppleton and
Mathieson12that the broad, structural features and cell dimensions of cellotetrose
may be correlated with those of cellulose I1 (from mercerization). They showed
that, in cellotetrose, the oligomers and the resultant sheets are not quarter-
staggered but are in register (full correspondence) with each other. Therefore,
provided that Poppleton and Mathieson’s basic assumption is valid, in cellulose
I1 the sheets are not quarter-staggered with relation to each other, as in cellulose
I, but are in register. As a result, in the conversion of cellulose I to cellulose I1
in the solid state the basic change in the structure of the crystallite within the
microfibrils must be a shift of adjacent sheets from a quarter-staggered relation
to full register. In the following,we shall show that the assumption is consistent
with experimental observations.
The mechanism of such a shift in concentrated alkali is related to the swelling
reactions investigated by Warwicker and colleague^.^^^ They provided sub-
stantial evidence that, under mercerizing or similar conditions, the sheets of
polyglucosan chains in cellulose were spread apart or separated as the alkali
hydroxides formed complexes with the constituent chain^.^.^,'^ Although
* As done by Gardner and Blackwell; the Miller indices of (liO), (110),and (020) in the unit cell
are set in the monoclinic system recommendedby the International Tables for X - R a y Crystallog-
raphy. In the old system, used by the majority of celluloseworkers, these correspond to (101),(lOi),
and (0021, respectively. Note that Warwicker and colleagues chose their sheets in the (110) plane,
whereas those of Gardner and Blackwell are in the (020) plane.
1338 TAKA1 A N D COLVIN

Warwicker and associates did not suggest translational movement of the sheets,
it is clear that the swelling and separation of the sheets in any particular domain
or crystallite would facilitate their movement into a lower free-energy position,
that of cellulose IL14 Because it is a lower free-energy position (approximately
-2 cal/g heat plus an undetermined increase in entropy), the sheets would tend
to remain in that position even when swelled again, thus accounting for the
well-established, essentially irreversible change from I to 11.'

Justification
When considering the plausibility of a shift like that suggested above, model
building is an aid. Two sheets of 6-1,Cpolyglucosan chains, associated laterally
as in the structure by Gardner and Blackwell? were constructed from space-
filling Fisher-Taylor-Hirschfelderatom models. When one sheet was placed
on top of the second in the quarter-stagger position, as in cellulose I, there was
a perceptible minimum in energy for that position as compared with small dis-
placements of the whole sheet from it. That is, the under surface of the upper
sheet fitted the upper surface of the lower sheet well when they were in the
quarter-stagger relation. However, in addition, when the upper sheet was dis-
placed so that it was in full correspondence with the lower sheet, as in cellotetrose
but with a small lateral movement, a second perceptible minimum in energy was
detected. This second minimum was at least as deep as the first, perhaps deeper.
Unfortunately, there seems to be no feasible, quantitative method at present
for estimating the depth of this minimum unless it is computer modeling which
is very sensitive to the parameters chosen. Nonetheless, the demonstrated
qualitative presence of the minimum provides plausibility, although not proof,
for the postulated shift. Furthermore, the necessity of the small, lateral dis-
placement of the sheets in order to reach the second minimum is consistent with
the well-known decrease of the 6 angle of the unit cell from 83' to 63' and its
implied shift in the relation of the component chains. Therefore from two as-
pects, atomic models lend credibility to the proposed shift.
Dependent upon the associated swelling in concentrated alkali, relative lon-
gitudinal displacement of the sheets in the crystallites would also cause an in-
crease in lateral disorder and an increase in reactivity of hydroxyl groups, both
of which have been repeatedly observed after the conversion of cellulose I to
cellulose 11.' In addition, such displacement is capable of explaining the change
in the relative intensities of meridional reflections of x-ray diffraction diagrams
of cellulose fibers, which previously suggested mechanisms could not do. Since
the postulated longitudinal shift, along the axis of the fiber, would clearly change
the periodicity of the crystallites, one would expect changes in the meridional
reflections on mercerization. These changes O C C U ~ . ~ , ~
Furthermore, such a shift of sheets is consistent with the changes of intensities
of bands which are observed in the infrared spectrum, particularly those asso-
ciated with the hydroxyl groups.15 As pointed out by Blackwell and Marches-
sault,l these changes are to be ascribed to secondary, conformational factors and
to different hydrogen-bonding networks which are formed after or during the
conversion. Even if all of the hydrogen bonds of cellulose remain confined to
a sheet, the (020) plane, shifting of the sheets will cause different secondary in-
teractions which will be reflected in the spectrum of cellulose II.15
 MERCERIZATION MECHANISMS 1339

The effect of temperature during mercerization on the macroscopic shrinkage

of the washed pellicles and on the extent of conversion of bacterial cellulose I
to cellulose I1 are shown in Figures 1and 2, respectively. Shrinkage is more than
70% and conversion to cellulose I1 is essentially complete if the temperature is
less than 40°C. Above this point, shrinkage and the extent of conversion de-
crease until above 90” there is little change in both. Shrinkage and the extent
of conversion of cellulose I to cellulose I1 are therefore associated, both decreasing
as the temperature of mercerization increases.
For extent of conversion to cellulose I1 as a function of temperature, these
results for bacterial cellulose are similar to those reported by Jeffries and War-
wicker for cotton3 and by Hayashi and Colleagues for ramie.4 All three series
of observations are easily explained by the assumptions that (a) the swelling
between sheets decreases as the temperature increases, thereby increasing re-
sistance to shifting2; (b) at any particular temperature and hydroxide concen-
tration, the resistance to shifting of the sheets varies from crystallite to crystallite.
Given these two conditions, the consequence would be a distribution between
the two forms of cellulose, which varies with temperature. Such a variable dis-
tribution is observed (Fig. 2, see also the l i t e r a t ~ r e ~ , ~ ) .
The temperature-dependent, macroscopic, isometric ‘shrinkage of the pellicles
of bacterial cellulose may also be explained, qualitatively, by the same two as-
sumptions. Differential shifting of the sheets within a crystallite and differing
degrees of conversion between crystallites will set up internal strains within the
initially straight microfibrils which will be minimized by coiling or convolution.
The consequent shortening of the microfibrils will cause an isometric shrinking
(and thickening) of the diameter of the pellicle. Since the degree of convolution
of the microfibrils will be cumulative with the extent of conversion of the crys-
tallites to cellulose 11, one would expect to find the observed correlation between
shrinkage and extent of conversion (Figs. 1and 2).

60 -

40 -

20 -

I I I I I I I I I I 1
0 20 40 60 80 100
Temp (“c1
Fig. 1. Percentage shrinkage of native bacterial cellulose pellicles as a function of the temperature
of mercerization for (a) (0) pellicles which were mercerized directly, without previous treatment
and (b) ( 0 )pellicles which were heated at 100°C for 2 hr in 18% NaOH before mercerization at the
indicated temperature. Note that at 90°C the shrinkage of the pellicles was 10% or less. At 2OoC
the shrinkage was 70% or a little more.
1340 TAKA1 AND COLVIN

Fig. 2. Representative x-ray diffraction photographs of bacterial cellulose pellicles after mer-
cerization at different temperatures. Parallel bars (11) indicate that the plane of the cellulose mem-
brane was parallel to the direction of the beam; perpendicular bars (1) indicate that the plane of
the membrane was perpendicular to the beam. Note that at 25°C conversion to cellulose I1 was nearly
complete; at loO°C there was little, if any, conversion.

The same two assumptions are also capable of explaining the “memory” of
previous treatments which is often displayed by samples of cellulose. As shown
in Figure 1,prior treatment of bacterial cellulose for 2 hr at 100°C in 18%NaOH
reduces the shrinkage during mercerization at intermediate temperatures by
35% although no differences in shrinkage are observed for both extremes of
temperature. Using the association established above, one may conclude that
the heating at 100°C for 2 hr hinders the conversion of cellulose I to cellulose I1
but does not prevent it completely, because at 0°C the shrinkage is as great as
without heating. The hindrance may be explained by assuming that during the
heating period at 100°C the intersheet swelling is r e d ~ c e dleading
,~ to greater
resistance to movement of the sheets within the crystallites than when heating
does not take place. At lower temperatures, where swelling is maximal, the
transient resistance is gone and conversion of the heated cellulose is as extensive
as that of the unheated. The effect of heating on the intersheet swelling of the
crystallites is recorded by (“remembered” in) the shape of the familiar hysteresis
loop (Fig. 1).
If the foregoing explanation of the effect of temperature on the mercerization
of cellulose is correct, it will be applicable to studies on the effect of tension on
extent of mercerization. Jeffries and Warwicker3 showed that in cotton the
degree of conversion to cellulose 11,for given concentrations of NaOH, was less
for samples under tension than under conditions of free swelling. In addition,
tension applied to the fibers after swelling had no effect. They interpreted the
effect of tension as a restriction on swelling but it is equally valid to assume that
the fibrillar tension partially prevents the shift of the sheets in the crystallites
which is necessary to form cellulose 11. The effect of tension is to restrict
 MERCERIZATION MECHANISMS 1341

movement of some sheets mechanically, thus hindering conversion to the second

form of cellulose. The effect of methanol or ethanol on mercerization of cellulose
may be interpreted in a similar way: the additive reduces the intersheet swelling,
increases the resistance to movement of the sheets, and therefore decreases
conversion to cellulose 11.

DISCUSSION
In the foregoing sections, it has been suggested that the mechanism of mer-
cerization of cellulose involves the progressive shift of sheets of polyglucosan
chains over one another in the crystallites of the microfibril. This notion explains
qualitatively all the changes observed when cellulose I alters to cellulose 11, in-
cluding some which are not consistent with previously proposed mechanisms.
The shift need not and does not involve changes in the original polarity of the
polyglucosan chains or require the solution of the cellulose. The mechanism
may be applied equally well to those types of native cellulose with an antiparallel
structure as to those with parallel structure like’Vuloniu.
The suggested mechanism is also applicable to mercerization of preferentially
oriented sheets of cellulose. As demonstrated recently,16selective, uniplanar
orientation of the crystallites of bacterial cellulose takes place when the swollen,
gel-like membranes are dried on a glass plate. This orientation tends to be re-
tained even after mercerization. Since the (1x0) plane of the crystallites tends
to be parallel to the membrane surface as a result of drying, subsequent relative
shifting of the sheets in the (020) plane will remain possible during mercerization
and the preferential orientation will be maintained, even when shrinkage is free.
When shrinkage is prevented by clamping, the latent tendency of the (020) planes
to shift relative to each other will produce a biaxially oriented sheet. Both effects
are observed.16
Relative displacement of the sheets in the (020) plane also is consistent with
the observed, initial loss of sharpness and the broadening of the diffraction line
of the (li0) plane.16 Whenever two (020) sheets slide over each other there will
be a simultaneous disturbance of the periodicity of the corresponding (1iO) plane
and a concomitant loss in total intensity of the line.
It may be necessary to emphasize that the present suggestion does not repu-
diate or invalidate previous ideas of a conformational change taking place during
mer~erization.~?~ It simply broadens and extends our understanding of the
molecular cause of such a conformational change. For instance, when the sheets
of cellulose chains shift over each other in the crystallite during mercerization,
it is certain that the shift must be accompanied by a conformational variation
in one or more elements of the chains. This is because the sheets are not uniform
over their surface, either in topography or chemical composition, and this
nonuniformity will be reflected in different interactions at different sites. These
different interactions will in turn be reflected in variations in, for instance, both
Raman and infrared spectra. Thus, the present idea is consistent with and
amplifies previous s~ggestions.~,5
The proposed mechanism of mercerization may be readily extended to explain
why samples of cellulose often show effects which reflect a “memory” of diverse
t r e a t m e n t ~ . ~IfJ ~an indicated treatment modifies irreversibly the molecular
structure of only a fraction of the crystallites or domains in the microfibrils of
1342 TAKA1 AND COLVIN

cellulose, this modification will be retained and may be reflected in the properties
of derived materials even though no changes are immediately apparent. Re-
tention of differences in molecular domains may well be the reason why indu-
bitable cellulose 111’s have recognizably different properties, depending on their
source.l5
The foregoing suggestion has one grave limitation, however: it gives no ad-
ditional insight into the continuing problem of why, during biosynthesis, most
sheets of cellulose are deposited in the metastable f ~ r m . ~Since
J ~ they may move
easily and irreversibly in concentrated alkali into the more stable cellulose I1
structure, a special enzymatic mechanism must be postulated to rationalize why
this movement is not accomplished during formation of the microfibril. The
molecular basis of this mechanism is unknown.
The proof or disproof of the foregoing suggestion would come best from a de-
finitive structure for mercerized Valonia cellulose. It is to be hoped that such
a structure will be reported soon.

References
1. J. Blackwell, R. H. Marchessault, R. T. O’Connor, D. W. Jones, 0. Ellefsen, and B. A. Tonnesen,
in Cellulose and its Derivatives (High Polymers, Vol. V), Part IV, 2nd ed., N. M. Bikales and L.
Segal, Eds., Wiley-Interscience, New York, 1971, Chap. 13.
2. J. 0. Warwicker and A. C. Wright, J. Appl. Polym. Sci., 11,659 (1967).
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I (Appl. Polym. Symp., 28), T. E. Timell, Ed., Wiley, New York-London, 1976, pp. 713-727.
5. R. A. Atalla, in Proceedings of the 8 t h Cellulose Conference, Part Z (Appl. Polym. Symp.,
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12. B. J. Poppleton and A. McL. Mathieson, Nature, 219,1046 (1968).
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Bikales and L. Segal, Eds., Wiley-Interscience, New York, 1971, Chap. 13.
14. B. G. Ranby, Acta Chem. Scand., 6,101,116,128 (1952).
15. H. J. Marrinan and J. Mann, J. Polym. Sci., 21,301 (1956).
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(1974).
17. V. E. Stockmann, Biopolymers, 11,251 (1972).

Received January 6,1977

Revised April 27,1977